Fungicidal mixtures

ABSTRACT

A fungicidal mixture, comprising at least one compound selected from 
     a) carbamates of the formula I,                    
      where T is CH or N, n is 0, 1 or 2 and R is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl, it being possible for the radicals R to be different if n is 2, 
     a 2 ) the oxime ether carboxylate of the formula II                    
      or 
     a 3 ) the oxime ether carboxamide of the formula III,                    
      and 
     b) a compound of the formula IV                    
     in a synergistically effective amount.

This application is a 371 of PCT/EP98/02875, filed May 15, 1998.

The present invention relates to a fungicidal mixture, comprising atleast one compound selected from

a₁) carbamates of the formula I,

 where T is CH or N, n is 0, 1 or 2 and R is halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, it being possible for the radicals R to be different ifn is 2,

a₂) the oxime ether carboxylate of the formula II

 or

a₃) the oxime ether carboxamide of the formula III,

 and

b) at least one compound of the formula IV,

 where the substituents X¹ to X⁵ and R¹ to R⁴ have the followingmeanings:

X¹ to X⁵ independently of each other are each hydrogen, halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-thioalkoxy, C₁-C₄-sulfonylalkyl, nitro, amino,N-C₁-C₄-carboxylamino, N-C₁-C₄-alkylamino;

R¹ is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkinyl,C₁-C₄-alkyl-C₃-C₇-cycloalkyl, it being possible for these radicals tocarry substituents selected from the group consisting of halogen, cyano,and C₁-C₄-alkoxy,

R² is a phenyl radical or a 5- or 6-membered saturated or unsaturatedheterocyclyl radical having at least one hetero atom selected from thegroup consisting of N, O and S, it being possible for the cyclicradicals to have one to three substituents selected from the groupconsisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₂-C₄-alkenyl,C₁-C₄-alkoxy-C₂-C₄-alkinyl,

R³ and R⁴ independently of each other are each hydrogen, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, N-C₁-C₄-alkylamino, C₁-C₄-haloalkyl orC₁-C₄-haloalkoxy

in a synergistically effective amount.

Moreover, the invention relates to methods for controlling harmful fungiusing mixtures of the compounds I, II and/or III and IV and to the useof the compounds I, II and/or III and IV for the preparation of suchmixtures.

The compounds of the formula I, their preparation and their activityagainst harmful fungi are disclosed in the literature (WO-A 96/01,256and 96/01,258).

The compounds of the formula II and III, their preparation and theiractivity against harmful fungi are disclosed in the literature (EP-A 253213, EP-A 398 692 and EP-A 477631).

The compounds of the formula IV and processes for their preparation aredescribed in WO-A 96/19442.

It was an object of the present invention to provide mixtures which havean improved activity against harmful fungi combined with a reduced totalamount of active ingredients applied (synergistic mixtures), with a viewto reducing the rates of application and to improving the spectrum ofaction of the known compounds.

Accordingly, we have found that this object is achieved by the mixturesdefined at the outset. Moreover, we have found that better control ofthe harmful fungi is possible by applying the compounds I and II and/orIII simultaneously together or separately, or by applying the compoundsI and II and/or III in succession, than when the individual compoundsare used.

The formula I represents in particular carbamates in which thecombination of the substituents corresponds to one row of the tablebelow:

TABLE 1 No. T R_(n) I.1 N 2-F I.2 N 3-F I.3 N 4-F I.4 N 2-Cl I.5 N 3-ClI.6 N 4-Cl I.7 N 2-Br I.8 N 3-Br I.9 N 4-Br I.10 N 2-CH₃ I.11 N 3-CH₃I.12 N 4-CH₃ I.13 N 2-CH₂CH₃ I.14 N 3-CH₂CH₃ I.15 N 4-CH₂CH₃ I.16 N2-CH(CH₃)₂ I.17 N 3-CH(CH₃)₂ I.18 N 4-CH(CH₃)₂ I.19 N 2-CF₃ I.20 N 3-CF₃I.21 N 4-CF₃ I.22 N 2,4-F₂ I.23 N 2,4-Cl₂ I.24 N 3,4-Cl₂ I.25 N 2-Cl,4-CH₃ I.26 N 3-Cl, 4-CH₃ I.27 CH 2-F I.28 CH 3-F I.29 CH 4-F I.30 CH2-Cl I.31 CH 3-Cl I.32 CH 4-Cl I.33 CH 2-Br I.34 CH 3-Br I.35 CH 4-BrI.36 CH 2-CH₃ I.37 CH 3-CH₃ I.38 CH 4-CH₃ I.39 CH 2-CH₂CH₃ I.40 CH3-CH₂CH₃ I.41 CH 4-CH₂CH₃ I.42 CH 2-CH(CH₃)₂ I.43 CH 3-CH(CH₃)₂ I.44 CH4-CH(CH₃)₂ I.45 CH 2-CF₃ I.46 CH 3-CF₃ I.47 CH 4-CF₃ I.48 CH 2,4-F₂ I.49CH 2,4-Cl₂ I.50 CH 3,4-Cl₂ I.51 CH 2-Cl, 4-CH₃ I.52 CH 3-Cl, 4-CH₃

Particular preference is given to the compounds I.12, I.23, I.32 andI.38.

In relation to the C═Y or C═CH or C═N double bonds, the compounds of theformulae I to III can be present in the E or the Z configuration (inrelation to the carboxylic acid function). Accordingly, they can be usedin the mixture according to the invention in each case either in theform of the pure E or Z isomers or in the form of an E/Z isomer mixture.

The E/Z isomer mixture or the Z isomer is preferably used, the Z isomerbeing especially preferred.

The C═N double bonds of the oxime ether groups in the side chain of thecompounds I to III can exist in each case in the form of pure E or Zisomers or as E/Z isomer mixtures. The compounds I to III can be used inthe mixtures according to the invention both as isomer mixtures and aspure isomers. With a view to their use, compounds I to III which areparticularly preferred are those where the terminal oxime ether group inthe side chain is in the cis configuration (OCH₃ to ZR′).

Owing to their basic character, the compounds I to III are capable offorming salts or adducts with inorganic or organic acids or with metalions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid and alkanoic acidssuch as acetic acid, trifluoroacetic acid, trichloroacetic acid andpropionic acid, and also glycolic acid, thiocyanic acid, lactic acid,succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid,alkylsulfonic acids (sulfonic acids having straight-chain or branchedalkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids oraryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl,which carry one or two sulfo groups), alkylphosphonic acids (phosphonicacids having straight-chain or branched alkyl radicals of 1 to 20 carbonatoms), arylphosphonic acids or aryldiphosphonic acids (aromaticradicals, such as phenyl and naphthyl, which carry one or two phosphonicacid radicals), it being possible for the alkyl or aryl radicals tocarry further substituents, for example p-toluenesulfonic acid,salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminum, tin and lead, and of thefirst to eighth subgroup, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. Especially preferred are themetal ions of the elements of the subgroups of the fourth period. Themetals can exist in the various valences which they can assume.

Among the compounds of the formula IV, those are preferred where X¹ is aC₁-C₄-haloalkyl group, in particular a trifluoromethyl group, and X² andX³ are hydrogen or a halogen group, in particular hydrogen. X⁴ and X⁵are preferably hydrogen, halogen (in particular C1 or F), C₁-C₄-alkoxy(in particular methoxy or ethoxy), C₁-C₄-alkylthio (in particularmethylthio or ethylthio), C₁-C₄-haloalkyl (in particulartrifluoromethyl) or C₁-C₄-haloalkoxy (in particular trifluoromethoxy).

Preferred substituents R¹ are C₁-C₄-alkyl (methyl, ethyl, n- andi-propyl and t-butyl), C₁-C₄-alkylene-C₃-C₇-cycloalkyl, C₁-C₄-alkenyl(in particular ethenyl, propenyl and butenyl, in particular those whichmay be substituted by halogen (preferably Cl)), propinyl, cyanomethyland methoxymethyl. Among the C₁-C₄-alkylene-C₃-C₇-cycloalkylsubstituents, preference is given in particular to methylene-substitutedcompounds, in particular methylenecyclopropyl, methylenecyclopentyl,methylenecyclohexyl and methylenecyclohexenyl. The rings of thesesubstituents may be substituted, preferably by halogen.

Suitable substituents R² are, in addition to phenyl (unsubstituted orsubstituted), in particular thienyl, pyrazolyl, pyrrolyl, imidazolyl,thiazolyl, furyl, pyridazinyl and pyrimidinyl. Preferred substituents onthese ring systems are halogen (in particular F and Cl), C₁-C₄-alkoxy(in particular methoxy) and C₁-C₄-alkyl (in particular methyl, ethyl).The number of the ring substituents may be 1 to 3, in particular 1 to 2.Particular preference is given to phenyl or substituted phenyl.

Preferred substituents R³ and R⁴ are hydrogen, F, Cl, methyl, ethyl,methoxy, thiomethyl and N-methylamino. R³ and R⁴ together mayadditionally form a grouping=O.

Preferred compounds of formula IV are shown in the tables of theabovementioned WO 96/019442. Among these, the compounds listed in TableII below are particularly preferred (R³ and R⁴ are each hydrogen).

TABLE II No. X¹ X² X³ X⁴ X⁵ R¹ R² II.1 CF₃ H H H H ethyl Ph-4-OMe II.2CF₃ H H H H methyl Ph-4-OMe II.3 CF₃ H H H H —CH₂-cPr 2-thienyl II.4 CF₃H H H H —CH₂-cPr 3-thienyl II.5 CF₃ H H H H —CH₂-cPr Ph-2,4-F₂ II.6 CF₃H H H H —CH₂-cPr Ph-2-F II.7 CF₃ H H H H —CH₂-cPr Ph-2-F-4-OMe II.8 CF₃H H H H —CH₂-cPr Ph-3-Me II.9 CF₃ H H H H —CH₂-cPr Ph-3-Me-4-OMe II.10CF₃ H H H H —CH₂-cPr Ph-4-F II.11 CF₃ H H H H —CH₂-cPr Ph-4-Me II.12 CF₃H H H H —CH₂-cPr Ph-4-OMe II.13 CF₃ H H H H —CH₂-cPr Ph II.14 CF₃ H H HH —CH₂—CH═CH₂ Ph II.15 CF₃ H H H H —CH₂—CH═CH₂ Ph-4-OMe II.16 CF₃ H H HH —CH₂—CH═CCl₂ Ph-4-OMe II.17 CF₃ H H H F —CH₂—CH₃ Ph-4-OMe II.18 CF₃ HH H F —CH₂CH₃ Ph II.19 CF₃ H H H F —CH₃ Ph-4-OMe II.20 CF₃ H H H F—CH₂-cPr Ph II.21 CF₃ H H H F —CH₂-cPr Ph-2-F II.22 CF₃ H H H F —CH₂-cPrPh-2,4-F₂ II.23 CF₃ H H H F —CH₂-cPr Ph-2-F-3-Me II.24 CF₃ H H H F—CH₂-cPr Ph-2-F-4-OMe II.25 CF₃ H H H F —CH₂-cPr Ph-3,5-Me₂ II.26 CF₃ HH H F —CH₂-cPr 3-methylpyra- zol-1-yl II.27 CF₃ H H H F —CH₂-cPr3-methyl- 2-thienyl II.28 CF₃ H H H F —CH₂-cPr 2-thienyl II.29 CF₃ H H HF —CH₂-cPr 3-thienyl II.30 CF₃ H H H F —CH₂—CHF₂ Ph-4-OMe II.31 CF₃ H HH F —CH₂—OCH₃ Ph-4-OMe II.32 CF₃ H H H F —CH₂—OCH₃ Ph II.33 CF₃ H H H F—CH₂CN Ph-4-Ome II.34 CF₃ H H H F —CH₂CN Ph II.35 CF₃ H H H F —CH₂—C≡CHPh II.36 CF₃ H H H F —CH₂—C≡CH Ph-4-OMe II.37 CF₃ H H H F —CH₂—C≡CHPh-2-F II.38 CF₃ H H H F —CH₂—C≡CH Ph-4-Me II.39 CF₃ H H H F —CH₂—C≡CH2-thienyl II.40 CF₃ H H H F —CH₂—C≡CH Ph-2-F-4-OMe II.41 CF₃ H H H Fi-propyl Ph II.42 CF₃ H H H F n-butyl Ph II.43 CF₃ H H H F n-propyl PhII.44 CF₃ H H H F t-butyl Ph II.45 CF₃ H H H Cl —CH₃ II.46 CF₃ H H H Cl—CH₂CN Ph-4-OMe II.47 CF₃ H H H Cl —CH₂—OMe Ph-4-OMe II.48 CF₃ H H H Cl—CH₂-cPr Ph II.49 CF₃ H H H Cl —CH₂-cPr 3-methylpyra- zol-1-yl II.50 CF₃H H H Cl —CH₂-cPr 2-thienyl II.51 CF₃ H H H Cl —CH₂-cPr Ph-2,4-F₂ II.52CF₃ H H H Cl —CH₂—C≡CH Ph-4-OMe II.53 CF₃ H H H CF₃ —CH₃ Ph-4-OMe II.54CF₃ H H H CF₃ —CH₂CH₂Cl Ph-4-OMe II.55 CF₃ H H H CF₃ —CH₂-cPr 2-thienylII.56 CF₃ H H H CF₃ —CH₂-cPr Ph-2-F-5-Me II.57 CF₃ H H H CF₃ —CH₂-cPrPh-4-OMe II.58 CF₃ H H H CF₃ —CH₂-cPr Ph II.59 CF₃ H H H OCH₃ —CH₂CH₃Ph-4-OMe II.60 CF₃ H H H OCH₃ —CH₂-cPr Ph-4-OMe II.61 CF₃ H H H OCH₃—CH₂-cPr Ph II.62 CF₃ H H H SCH₃ —CH₂-cPr Ph II.63 CF₃ H H H SCH₃—CH₂-cPr Ph-4-OMe II.64 CF₃ H H Cl F —CH₂—CH₂Cl Ph II.65 CF₃ H H Cl F—CH₂—CH═CH₂ Ph-4-OMe II.66 CF₃ H H Cl F —CH₂-cPr 2-thienyl II.67 CF₃ H HCl F —CH₂-cPr Ph-2-F II.68 CF₃ H H Cl F —CH₂-cPr Ph II.69 CF₃ H H Cl F—CH₂-cPr Ph-2-F-5-Me II.70 CF₃ H H Cl Cl —CH₂—CH═CH₂ Ph-4-OMe II.71 CF₃H H Cl Cl —CH₂CH₂Cl Ph II.72 CF₃ H H Cl Cl —CH₂CH₃ Ph-2-F-5-Me II.73 CF₃H H Cl Cl —CH₂-cPr Ph-3,5-Me₂ II.74 CF₃ H H SCH₃ F —CH₂-cPr Ph-4-OMeII.75 CF₃ H H OCH₃ F —CH₂-cPr Ph-4-OMe II.76 CF₃ H F H H —CH₂-cPr PhII.77 CF₃ H F H H —CH₂—CH₃ Ph-4-OMe II.78 CF₃ H H F F —CH₂CH₃ Ph II.79CF₃ H H F F —CH₂—CH₂Cl Ph-2-F-5-Me II.80 CF₃ H H F F —CH₂—OCH₃ Ph-4-OMeII.81 CF₃ H H F F —CH₂-cPr Ph II.82 CF₃ H H F F —CH₂-cPr 3-methylpyra-zol-1-yl II.83 CF₃ H H F F —CH₂-cPr 3-methyl- 2-thienyl II.84 CF₃ H H FF —CH₂-cPr Ph-2-F-3-Me II.85 CF₃ H H F F —CH₂-cPr Ph-2-F-4-OMe II.86 CF₃H H F F —CH₂-cPr Ph-2-F-5-Me II.87 CF₃ H H F F —CH₂-cPr Ph-4-OMe II.88CF₃ H H F F —CH₂-cPr Ph-4F II.89 CF₃ H H F F i-propyl Ph-4-OMe II.90 CF₃H H F F n-Butyl Ph-4-OMe II.91 CF₃ H H F F —CH₂—C≡CH Ph-4-OMe II.92 CF₃H H CF₃ F —CH₃ Ph-4-OMe II.93 CF₃ H H CF₃ F —CH₂—CH═CH₂ Ph II.94 CF₃ H HCF₃ F —CH₂-cPr Ph II.95 CF₃ H H Cl Cl —CH₂—CHxe-3 Ph II.96 CF₃ H H F H—CH₂-cPr Ph-4-F II.97 CF₃ H H Cl Cl —CH₂-cHex Ph II.98 CF₃ H H H F—CH₂—SCH₃ Ph II.99 CF₃ H H H F —CH₂—SOCH₃ Ph II.100 CF₃ H H H F—CH₂—SO₂CH₃ Ph II.101 CF₃ H H H F —CH₂—NHMe Ph II.102 CF₃ H H H FCH₂—CONH₂ Ph II.103 CF₃ H H H F CH₂CON(CH₃)₂ Ph

In the table above, cPr is cyclopropyl, cHxe-n is cyclohexenylunsaturated in position n, c-Hex is cyclohexyl and Ph is phenyl.

Particular preference is given to compounds IV in which R¹ is a radicalCH₂-cPr and R² is an unsubstituted or substituted phenyl radical. Amongthese, preference is given to compounds in which X⁴ and X⁵ are eachhalogen, preferably F. The physical data of these compounds andprocesses for their preparation are given in the abovementioned WO94/19442.

When preparing the mixtures, it is preferred to employ the pure activeingredients I, II and/or III and IV, to which further ingredients activeagainst harmful fungi or other pests, such as insects, arachnids ornematodes, or else herbicidal or growth-regulating active ingredients orfertilizers can be admixed, if so required.

The mixtures of the compounds I, II and/or III and IV, or thesimultaneous joint or separate use of the compounds I, II and/or III andIV, have outstanding action against a wide spectrum of phytopathogenicfungi, in particular from the classes of the Ascomycetes,Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them actsystemically and can therefore be employed as folia- and soil-actingfungicides.

They are especially important for controlling the large number of fungiin a variety of crop plants, such as cotton, vegetable species (e.g.cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize,fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugarcane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawn, Ustilago species in cereals and sugar cane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinerea (gray mold) in strawberries, vegetables,ornamentals and grapevines, Cercospora arachidicola in groundnuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Pseudoperonospora species in cucurbits and hops, Plasmopara viticola ingrapevines, Alternaria species in vegetables and fruit and Fusarium andVerticillium species.

Furthermore, they can be used in the protection of materials (e.g. inthe protection of wood), for example against Paecilomyces variotii.

The compounds I, II and/or III and IV can be applied simultaneouslytogether or separately or in succession, the sequence, in the case ofseparate application, generally not having any effect on the result ofthe control measures.

The compounds I, II and/or III and IV are usually used in a weight ratioof from 0.01:1 to 1:1, preferably from 0.03:1 to 0.5:1, in particularfrom 0.05:1 to 0.5:1 (IV:I, II and/or III).

The application rates of the mixtures according to the invention are, inthe case of the compounds I, II and/or III, from 0.005 to 0.5 kg/ha,preferably from 0.05 to 0.5 kg/ha, in particular from 0.05 to 0.2 kg/ha,depending on the nature of the desired effect.

Correspondingly, in the case of the compounds IV, the application ratesare generally from 0.001 to 0.2 kg/ha, preferably from 0.001 to 0.1kg/ha, in particular from 0.005 to 0.05 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 100 g/kg of seed, preferably from 0.01 to 50 g/kg, inparticular from 0.01 to 10 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II or of the mixtures of thecompounds I, II and/or III and IV is effected by spraying or dusting theseeds, the plants or the soils before or after sowing of the plants, orbefore or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I, II and/or III and IV, can be formulated for example in theform of ready-to-spray solutions, powders and suspensions or in the formof highly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for broadcasting orgranules, and applied by spraying, atomizing, dusting, broadcasting orwatering. The use form depends on the intended purpose; in any case, itshould ensure as fine and uniform as possible a distribution of themixture according to the invention.

The formulations are prepared in a manner known per se, e.g. by addingsolvents and/or carriers. It is usual to admix inert additives, such asemulsifiers or dispersants, with the formulations.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, e.g. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-,hepta- and octadecanols orof fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, laurylalcohol polyglycol ether acetate, sorbitol esters, lignosulfite wasteliquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor jointly grinding the compounds I and II or III or IV or the mixtureof the compounds I and II, III or IV with a solid carrier.

Granules (e.g. coated granules, impregnated granules or homogeneousgranules) are usually prepared by binding the active ingredient, oractive ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials, andfertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably from 0.5 to 90% by weight, of one of the compounds I, II, IIIand/or IV or of the mixture of the compounds I, II and/or III and IV.The active ingredients are employed in a purity of from 90% to 100%,preferably from 95% to 100% (according to NMR spectrum or HPLC).

The compounds I, II and/or III or IV, or the mixtures, or thecorresponding formulations, are applied by treating the harmful fungi orthe plants, seeds, soils, areas, materials or spaces to be kept freefrom them with a fungicidally effective amount of the mixture, or thecompounds I, II and/or III and IV in the case of separate applications.Application can be effected before or after infection by the harmfulfungi.

The fungicidal activity of the compound and the mixtures is demonstratedby the following experiments:

The active ingredients, separately or together, are formulated as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying anddispersing action, based on ethoxylated alkylphenols) and 10% by weightof Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fattyalcohols) and diluted with water to give the desired concentration.

USE EXAMPLE 1 Activity Against Powdery Mildew of Wheat

Leaves of wheat seedlings cv. “Frühgold” which had been grown in potswere sprayed to runoff point with an aqueous preparation of activeingredient which had been prepared from a stock solution comprising 10%of active ingredient, 63% of cyclohexanone and 27% of emulsifier and, 24hours after the spray coating had dried on, dusted with spores ofpowdery mildew of wheat (Erysiphe graminis forma specialis tritici). Thetest plants were subsequently placed in a greenhouse at from 20 to 240°C. and a relative atmospheric humidity of 60 to 90%. After 7 days, theextent of mildew development was determined visually as % infection ofthe total leaf area.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The expectedefficacies of the mixtures of the active ingredients are determinedusing Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)] and comparedwith the observed efficacies.

Colbys formula:

E=x+y+z−x·y·z/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active ingredients A, B and C at the concentrationsa, b and c

x efficacy, expressed in % of the untreated control, when using activeingredient A at a concentration of a

y efficacy, expressed in % of the untreated control, when using activeingredient B at a concentration of b

z efficacy, expressed in % of the untreated control, when using activeingredient C at a concentration of c

The efficacy (E) is calculated as follows using Abbot's formula:

 E=(1−α)·100/β

α corresponds to the fungal infection of the treated plants in % and

β corresponds to the fungal infection of the untreated (control) plantsin %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The test results are shown in Tables 2 and 3 below.

TABLE 2 Concentration of ac- tive ingredient in Efficacy in % Active thespray liquor in of the un- Ex. ingredient ppm treated control 1V Control(100% infection) 0 (untreated) 2V Compound I.32 0.5 10 0.125 0 3VCompound II 0.125 0 4V Compound III 0.125 20 5V Compound II.81 0.5 700.125 70

TABLE 3 Observed Calculated Mixtures according to the invention efficacyefficacy *) 0.5 ppm I.32 97 73 + 0.5 ppm II.81 (Mixture 1:1) 0.125 ppmI.32 93 70 + 0.125 ppm II.81 (Mixture 1:1) 0.125 ppm II 90 70 + 0.125ppm II.81 (Mixture 1:1) 0.125 ppm III 97 76 + 0.125 ppm II.81 (Mixture1:1)

*) calculated using Colby's formula

The test results show that for all mixing ratios the observed efficacyis higher than the efficacy which had been calculated beforehand usingColby's formula.

What is claimed is:
 1. A fungicidal composition comprisingsynergistically effective amounts of a component A) and a component B),wherein a) component A is a₁) at least one compound selected from agroup consisting of carbamates of formula I,

 where T is CH or N, n is 0, 1 or 2 and R is halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, and where the radicals R are identical or different ifn is 2, and optionally one or both of the following compounds: a₂) anoxime ether carboxylate of formula II

 and a₃) an oxime ether carboxamide of formula III,

 and b) component B is at least one compound of formula IV

 wherein X¹ is C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy; X² and X³ are eachhydrogen; X⁴ and X⁵ are independently of each other halogen; R¹ isC₁-C₄-alkylene-C₃-C₇-cycloalkyl; R² is a phenyl radical which isunsubstituted or substituted by one to three substituents selected fromthe group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-ha-loalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₂-C₄-alkenyl andC₁-C₄-alkoxy-C₂-C₄-alkinyl, R³ is hydrogen, and R⁴ is hydrogen, halogen,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, N-C₁-C₄-alkylamino,C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy.
 2. The composition defined in claim1, wherein component A comprises the oxime ether carboxylate of formulaII or the oxime ether carboxamide of formula III.
 3. The compositiondefined in claim 1, wherein component A comprises the oxime ethercarboxylate of formula II and the oxime ether carboxamide of formulaIII.
 4. A method for controlling harmful fungi, which comprises treatingthe harmful fungi, their habitat or plants, seeds, soils, areas,materials or spaces to be kept free from said fungi with synergisticallyeffective amounts of component A and component B, wherein the componentsA and B are as set forth in claim
 1. 5. The method of claim 4, whereinthe component A is applied in an amount of from 0.005 to 0.5 kg/ha. 6.The method of claim 5, wherein the component B is applied in an amountof from 0.001 to 0.2 kg/ha.
 7. The method of claim 4, wherein thecomponent A is applied in an amount of from 0.005 to 0.5 kg/ha.
 8. Themethod of claim 4, wherein the component B is applied in an amount offrom 0.001 to 0.2 kg/ha.
 9. The method claim 4, wherein component Acomprises the oxime ether carboxylate of formula II or the oxime ethercarboxamide of formula III.
 10. The method of claim 9, wherein thecomponent A is applied in an amount of from 0.005 to 0.5 kg/ha.
 11. Themethod of claim 9, wherein the component B is applied in an amount offrom 0.001 to 0.2 kg/ha.
 12. The method claim 4, wherein component Acomprises the oxime ether carboxylate of formula II and the oxime ethercarboxamide of formula III.
 13. The method of claim 12, wherein thecomponent A is applied in an amount of from 0.005 to 0.5 kg/ha.
 14. Themethod of claim 12, wherein the component B is applied in an amount offrom 0.001 to 0.2 kg/ha.